US2009137549A1PendingUtilityA1

Novel compounds useful for the treatment of degenerative & inflamatory diseases

Assignee: EDWARD PAUL JOHNPriority: Nov 9, 2006Filed: Nov 8, 2007Published: May 28, 2009
Est. expiryNov 9, 2026(~0.3 yrs left)· nominal 20-yr term from priority
A61P 29/00C07D 487/04A61P 19/10A61P 19/02
45
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Claims

Abstract

The present invention relates to compounds that are inhibitors of PDE1A, a phosphodiesterase that is involved in the modulation of the degradation of cartilage, joint degeneration and diseases involving such degradation and/or inflammation.

Claims

exact text as granted — not AI-modified
1 . A compound according to formula Ia, Ib, Ic, Id, Ie, If, Ig, or Ih: 
       
         
           
           
               
               
           
         
         wherein: 
         X represents a carbon-carbon bonded nitrogen-containing heterocycloalkyl group; 
         B represents substituted or unsubstituted C 1 -C 6  alkyl, or C 1 -C 6  haloalkyl;
 or B represents substituted or unsubstituted cycloalkyl, heterocycloalkyl, cycloalkylalkyl or heterocycloalkylalkyl; 
 or B represents substituted or unsubstituted aralkyl, aryl or heteroaryl; 
 or with respect to a compound according to the formulae Ia or Ig, B further includes H, NO 2 , C 1 -C 6  alkyl, halo, —CO-aryl, —CO-heteroaryl, —CO—N(R 10 )-aryl, or CO—N(R 10 )-heteroaryl; 
 
         Y represents a bond, substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl; 
         the group B—(CH 2 )n-, B—CO—, B—N(R 10 )CO—, B—SO 2 —, B—OCO—, B—N(R 10 )SO 2 —, B—Y— or B—NR 10 -D(R 9 )— is linked to X via a nitrogen atom within the X group; 
         D represents CH or N, with the proviso that when D represents CH, R 9  represents —NO 2  and when D represents N, R 9  represents CN; 
         R 1  represents H, C 1 -C 6  alkyl, (CH 2 )n-aryl, cycloalkyl or a —C 1 -C 6  alkyl-cycloalkyl group, each of which may optionally be substituted with one or more groups selected from halogen, CN, CF 3 , —NR 4 R 5 , —NR 5 COR 4 , —CONR 4 R 5 , —NR 5 SO 2 R 4 , —SO 2 NR 5 R 4 , C 1 -C 6  alkyl, C 1 -C 6  alkoxy, —COR 4 , —CO 2 R 4 , or —SO 2 R 4 ; 
         R 2  represents H, C 1 -C 6  alkyl, cycloalkyl, heterocycloalkyl, cycloalkylalkyl, (CH 2 )n-aryl, or a heteroaryl group, each of which may optionally be substituted with one or more groups selected from halogen, CN, —NR 4 R 5 , —NR 5 COR 4 , —CONR 4 R 5 , —NR 5 SO 2 R 4 , —SO 2 NR 5 R 4 , C 1 -C 6  alkyl, —C 1 -C 6  haloalkyl, C 1 -C 6  alkoxy, —C 1 -C 6  haloalkoxy, —COR 4 , —CO 2 R 4 , or SO 2 R 4 ; 
         R 3  represents H, halogen, C 1 -C 6  alkyl, cycloalkyl, (CH 2 )n-aryl, aryl, or a heteroaryl group, each of which may optionally be substituted with one or more groups selected from halogen, CN, —NR 4 R 5 , —NR 5 COR 4 , —CONR 4 R 5 , —NR 5 SO 2 R 4 , —SO 2 NR 5 R 4 , C 1 -C 6  alkyl, C 1 -C 6  haloalkyl, C 1 -C 6  alkoxy, C 1 -C 6  haloalkoxy, COR 4 , CO 2 R 4 , or SO 2 R 4 ; 
         R 4  represents H, C 1 -C 6  alkyl, C 1 -C 6  haloalkyl, cycloalkyl, or heterocycloalkyl; 
         R 5  represents H, C 1 -C 6  alkyl, or cycloalkyl; 
         R 9  represents CN or NO 2 ; 
         R 10  represents H or C 1 -C 6  alkyl; and 
         each “n” independently represents 0, 1, 2 or 3; 
       
       or a pharmaceutically acceptable salt thereof or isotopic variants thereof, stereoisomers or tautomers thereof. 
     
     
         2 . A compound according to  claim 1  wherein X is selected from piperidine, pyrrolidine and azetidine. 
     
     
         3 . A compound according to  claim 1  wherein the compound is according to formulae IIa, IIb, IIc, IId, IIe, IIf, IIg, or IIh: 
       
         
           
           
               
               
           
         
         wherein B, Y, D, R 2 , R 3  and R 9  are as in  claim 1 ; R 10  is H or Me; or a pharmaceutically acceptable salt, hydrate, solvate or prodrug thereof or isotopic variants thereof, stereoisomers or tautomers thereof. 
       
     
     
         4 . (canceled) 
     
     
         5 . A compound according to  claim 1  wherein R 2  is C 1 -C 6  alkyl, cycloalkyl, aryl, heteroaryl or heterocycloalkyl. 
     
     
         6 . A compound according to  claim 1  wherein R 2  is Me, i-Pr, t-Bu, cyclohexyl, cyclopentyl, cyclobutyl, phenyl, 4-fluorophenyl, pyridyl or pyrrolidinyl. 
     
     
         7 . A compound according to  claim 1  wherein R 3  is H or C 1 -C 6  alkyl. 
     
     
         8 . A compound according to  claim 1  wherein B is C 1 -C 6  alkyl, C 1 -C 6  haloalkyl, cycloalkyl, cycloalkylalkyl, heterocycloalkylalkyl, aralkyl, heteroarylalkyl, or heterocycloalkyl. 
     
     
         9 . A compound according to  claim 1  wherein B is n-Bu, t-Bu, Me, CF 3 , 2,2-dimethylpropyl, 3,3,3-trifluoropropyl, cyclohexyl, cyclopentyl, cyclobutyl, cyclopropyl, cyclohexylmethyl, benzyl, 4-fluorobenzyl, 3,4-dichlorobenzyl, alpha-methylbenzyl, piperidinyl, or tetrahydropyranyl. 
     
     
         10 . A compound according to  claim 1  wherein B is unsubstituted or substituted aryl. 
     
     
         11 . A compound according to  claim 1  wherein
 B is phenyl unsubstituted or substituted with one or more groups selected from halogen, CN, —NO 2 , NR 4 R 5 , NR 5 COR 4 , CONR 4 R 5 , NR 5 SO 2 R 4 , SO 2 NR 5 R 4 , C 1 -C 6  alkyl, C 1 -C 6  haloalkyl, C 1 -C 6  alkoxy, C 1 -C 6  haloalkoxy, heterocycloalkylalkyl, COR 4 , CO 2 R 4 , and SO 2 R 4 ; or   B is phenyl substituted with substituted or unsubstituted aryl, cycloalkyl, heterocycloalkyl or heteroaryl.   
     
     
         12 . A compound according to  claim 1  wherein
 B is heteroaryl unsubstituted or substituted with one or more groups selected from halogen, CN, —NO 2 , NR 4 R 5 , NR 5 COR 4 , CONR 4 R 5 , NR 5 SO 2 R 4 , SO 2 NR 5 R 4 , C 1 -C 6  alkyl, C 1 -C 6  haloalkyl, C 1 -C 6  alkoxy, C 1 -C 6  haloalkoxy, heterocycloalkylalkyl, COR 4 , CO 2 R 4 , and SO 2 R 4 ; or   B is heteroaryl substituted with substituted or unsubstituted aryl, cycloalkyl, heterocycloalkyl or heteroaryl.   
     
     
         13 . A compound according to  claim 1  wherein B is phenyl substituted with one or more groups selected from Me, Et, i-Pr, n-Bu, t-Bu, F, Cl, CF 3 , OMe, OEt, OCF 3 , OCHF 2 , CN, —NO 2 , CO 2 Me, NHAc, NH 2 , NMe 2 , COMe, NHSO 2 Me, NHSO 2 Et, and NHSO 2 —(CH 2 ) 4 -Me. 
     
     
         14 . A compound according to a  claim 1  wherein B is phenyl substituted with piperazin-1-yl, N-methylpiperazin-1-yl, N-isopropylpiperazin-1-yl, morpholin-1-yl, piperidin-1-yl, pyrrolidin-1-yl, or morpholin-1-ylmethyl. 
     
     
         15 . A compound according to  claim 1  wherein B is substituted or unsubstituted heteroaryl. 
     
     
         16 . A compound according to any one of  claims 1 - 3  wherein the compound is according to formulae Ig, or IIg; and the group B—Y— is selected from 
       
         
           
           
               
               
           
         
         wherein each one of R 8c  or R 8d  is independently selected from H, halogen, CN, —NO 2 , NR 4 R 5 , NR 5 COR 4 , CONR 4 R 5 , NR 5 SO 2 R 4 , SO 2 NR 5 R 4 , COR 4 , CO 2 R 4 , and SO 2 R 4 , or 
         each one of R 8c  or R 8d  is independently selected from C 1 -C 6  alkyl, C 1 -C 6  haloalkyl, C 1 -C 6  alkoxy, and C 1 -C 6  haloalkoxy, or 
         each one of R 8c  or R 8d  is independently selected from heterocycloalkylalkyl, cycloalkyl, heterocycloalkyl, heterocycloalkylphenyl, aryl and heteroaryl; 
         R 8e  is selected from H, C 1 -C 6  alkyl, and C 1 -C 6  haloalkyl; or 
         R 8e  is selected from heterocycloalkylalkyl, cycloalkyl, heterocycloalkyl, heterocycloalkylphenyl, aryl or heteroaryl; and each of subscript m1 and m2 is independently selected from 0, 1, and 2. 
       
     
     
         17 . A compound according to  claim 16  wherein each of R 8c  or R 8d  is selected from H, halogen, C 1 -C 6  alkyl, C 1 -C 6  haloalkyl, heterocycloalkylalkyl, cycloalkyl, heterocycloalkyl, heterocycloalkylphenyl, aryl or heteroaryl. 
     
     
         18 . A compound according to any one of  claims 1 - 3  wherein the compound is according to formulae Ig, or IIg; and the group B—Y— is selected from 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
         19 . A compound according to  claim 1  wherein the compound is according to formulae IVa, IVb, IVc or IVd: 
       
         
           
           
               
               
           
         
         wherein R 8a  and R 8b  are independently selected from H, halogen, CN, —NO 2 , NR 4 R 5 , NR 5 COR 4 , CONR 4 R 5 , NR 5 SO 2 R 4 , SO 2 NR 5 R 4 , C 1 -C 6  alkyl, C 1 -C 6  haloalkyl, C 1 -C 6  alkoxy, C 1 -C 6  haloalkoxy, COR 4 , CO 2 R 4 , SO 2 R 4 , heterocycloalkylalkyl, cycloalkyl, heterocycloalkyl. 
       
     
     
         20 . A compound according to  claim 19  wherein each of R 8a  or R 8b  is selected from H, C 1 -C 6  alkyl, halo, CN, C 1 -C 6  alkoxy, C 1 -C 6  haloalkyl, C 1 -C 6  haloalkoxy, amino, dialkylamino, heterocycloalkyl, and heterocycloalkylalkyl. 
     
     
         21 . (canceled) 
     
     
         22 . (canceled) 
     
     
         23 . (canceled) 
     
     
         24 . (canceled) 
     
     
         25 . (canceled) 
     
     
         26 . (canceled) 
     
     
         27 . (canceled) 
     
     
         28 . (canceled) 
     
     
         29 . (canceled) 
     
     
         30 . (canceled) 
     
     
         31 . (canceled) 
     
     
         32 . (canceled) 
     
     
         33 . A compound according to  claim 1  wherein the compound is according to formulae VIIIa, VIIIb, VIIIc or VIIId: 
       
         
           
           
               
               
           
         
         wherein R 8a  and R 8b  are independently selected from H, halogen, CN, —NO 2 , NR 4 R 5 , NR 5 COR 4 , CONR 4 R 5 , NR 5 SO 2 R 4 , SO 2 NR 5 R 4 , C 1 -C 6  alkyl, C 1 -C 6  haloalkyl, C 1 -C 6  alkoxy, C 1 -C 6  haloalkoxy, COR 4 , CO 2 R 4 , SO 2 R 4 , cycloalkyl, heterocycloalkyl, heterocycloalkylalkyl heterocycloalkylphenyl, aryl or heteroaryl. 
       
     
     
         34 . A compound according to  claim 33  wherein R 8a  and R 8b  are independently selected from H, C 1 -C 6  alkyl, halo, CN, C 1 -C 6  alkoxy, C 1 -C 6  haloalkyl, C 1 -C 6  haloalkoxy, amino, dialkylamino, heterocycloalkyl, and heterocycloalkylalkyl. 
     
     
         35 . (canceled) 
     
     
         36 . (canceled) 
     
     
         37 . (canceled) 
     
     
         38 . (canceled) 
     
     
         39 . (canceled) 
     
     
         40 . (canceled) 
     
     
         41 . (canceled) 
     
     
         42 . (canceled) 
     
     
         43 . (canceled) 
     
     
         44 . (canceled) 
     
     
         45 . (canceled) 
     
     
         46 . (canceled) 
     
     
         47 . (canceled) 
     
     
         48 . (canceled) 
     
     
         49 . (canceled) 
     
     
         50 . (canceled) 
     
     
         51 . (canceled) 
     
     
         52 . (canceled) 
     
     
         53 . (canceled) 
     
     
         54 . (canceled) 
     
     
         55 . (canceled) 
     
     
         56 . (canceled) 
     
     
         57 . (canceled) 
     
     
         58 . (canceled) 
     
     
         59 . (canceled) 
     
     
         60 . (canceled) 
     
     
         61 . (canceled) 
     
     
         62 . (canceled) 
     
     
         63 . (canceled) 
     
     
         64 . A compound according to  claim 1  wherein the compound is according to formulae XXa, XXb, XXc or XXd: 
       
         
           
           
               
               
           
         
       
       wherein R 8a  and R 8b  are independently selected from H, CN, —NO 2 , NR 4 R 5 , NR 5 COR 4 , CONR 4 R 5 , NR 5 SO 2 R 4 , SO 2 NR 5 R 4 , C 1 -C 6  alkyl, C 1 -C 6  haloalkyl, C 1 -C 6  alkoxy, C 1 -C 6  haloalkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted cycloalkylalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted heterocycloalkylalkyl, substituted or unsubstituted heteroaryl, substituted or unsubstituted aralkyl, COR 4 , CO 2 R 4 , and SO 2 R 4 . 
     
     
         65 . A compound according to  claim 64  wherein R 8a  and R 8b  are independently selected from H, C 1 -C 6  alkyl, halo, CN, C 1 -C 6  alkoxy, C 1 -C 6  haloalkyl, C 1 -C 6 haloalkoxy, amino, dialkylamino, heterocycloalkyl, and heterocycloalkylalkyl. 
     
     
         66 . (canceled) 
     
     
         67 . (canceled) 
     
     
         68 . A compound according to  claim 64  wherein R 8a  is H, Me, NMe 2 , Cl or F; and R 8b  is H, Me, Cl or F. 
     
     
         69 . A compound according to  claim 64  wherein R 8a  is H; and R 8b  is H, Me, Cl, F, NMe 2 , OMe, i-Pr, t-Bu, OCF 3 , CF 3 , CN, morpholin-1-yl, piperazin-1-yl, N-methylpiperazin-1-yl or N-isopropylpiperazin-1-yl. 
     
     
         70 . (canceled) 
     
     
         71 . (canceled) 
     
     
         72 . A compound according to  claim 1  wherein the compound is according to formulae XXIVa, XXIVb, XXIVc or XXIVd: 
       
         
           
           
               
               
           
         
       
       wherein Y is substituted or unsubstituted heteroaryl; and B is selected from H, C 1 -C 6  alkyl, C 1 -C 6  haloalkyl, halo, —CN, NO 2 , aryl, heteroaryl, cycloalkyl, cycloalkylalkyl, heterocycloalkyl, heterocycloalkylalkyl, heterocycloalkylphenyl, and aralkyl. 
     
     
         73 . (canceled) 
     
     
         74 . A compound according to  claim 72  wherein B is selected from pyridyl, pyrimidyl, pyrazinyl, quinolinyl, isoquinolinyl, benzimidazolyl, benzoxazolyl, benzthiazolyl, benz[1,3]dioxalyl, thiophenyl, pyrrolidinyl, furanyl, triazolyl, thiazolyl, imidazolyl, oxazolyl, oxadiazolyl, and tetrazolyl. 
     
     
         75 . A compound according to  claim 72  wherein B is selected from H, Me, t-Bu, F, Cl, CF 3 , —CN, NO 2 , Ph, morpholin-1-yl, piperidin-1-yl, piperazin-1-yl, N-Me-piperazin-1-yl, N-i-Pr-piperazin-1-yl, morpholinylmethyl, piperidinylmethyl, piperazinylmethyl, N-Me-piperazinylmethyl, N-i-Pr-piperazinylmethyl, morpholinylphenyl, piperidinylphenyl, piperazinylphenyl, N-Me-piperazinylphenyl, and N-i-Pr-piperazinylphenyl. 
     
     
         76 . A compound according to  claim 72  wherein the group B—Y— is selected from 
       
         
           
           
               
               
           
         
         wherein each one of R 8c  or R 8d  is independently selected from H, halogen, CN, —NO 2 , NR 4 R 5 , NR 5 COR 4 , CONR 4 R 5 , NR 5 SO 2 R 4 , SO 2 NR 5 R 4 , SO 2 R 4 , COR 4 , CO 2 R 4 , and SO 2 R 4 , or 
         each one of R 8c  or R 8d  is independently selected from C 1 -C 6  alkyl, C 1 -C 6  haloalkyl, C 1 -C 6  alkoxy, and C 1 -C 6  haloalkoxy, or 
         each one of R 8c  or R 8d  is independently selected from heterocycloalkylalkyl, cycloalkyl, heterocycloalkyl, heterocycloalkylphenyl, aryl and heteroaryl; 
         R 8e  is selected from H, C 1 -C 6  alkyl, and C 1 -C 6  haloalkyl; or 
         R 8e  is selected from heterocycloalkylalkyl, cycloalkyl, heterocycloalkyl, heterocycloalkylphenyl, aryl or heteroaryl; and 
         each of subscript m1 and m2 is independently selected from 0, 1, and 2. 
       
     
     
         77 . A compound according to  claim 76  wherein each of R 8c  or R 8d  is independently selected from H, Me, t-Bu, F, Cl, CF 3 , Ph, —CN, NO 2 , morpholin-1-yl, piperidin-1-yl, piperazin-1-yl, N-Me-piperazin-1-yl, N-i-Pr-piperazin-1-yl, morpholinylmethyl, piperidinylmethyl, piperazinylmethyl, N-Me-piperazinylmethyl, N-i-Pr-piperazinylmethyl, morpholinylphenyl, piperidinylphenyl, piperazinylphenyl, N-Me-piperazinylphenyl, and N-i-Pr-piperazinylphenyl; and each of subscript m1 and m2 is independently selected from 1 and 2. 
     
     
         78 . A compound according to  claim 72  wherein the group B—Y— is selected from 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
         79 . (canceled) 
     
     
         80 . (canceled) 
     
     
         81 . (canceled) 
     
     
         82 . (canceled) 
     
     
         83 . A compound according to  claim 1  wherein the compound is according to formulae XXVIIIa, XXVIIIb, XXVIIIc or XXVIIId: 
       
         
           
           
               
               
           
         
       
       wherein B is selected from C 1 -C 6  alkyl, C 1 -C 6  haloalkyl, C 1 -C 6  alkoxy, C 1 -C 6  haloalkoxy, substituted or unsubstituted cycloalkyl, substituted or unsubstituted cycloalkylalkyl, substituted or unsubstituted heterocycloalkyl, substituted or unsubstituted heterocycloalkylalkyl, substituted or unsubstituted heteroaryl and substituted or unsubstituted aralkyl; and the group D-R 9  is N—CN or CH—NO 2 . 
     
     
         84 . (canceled) 
     
     
         85 . A compound according to  claim 83  wherein B is selected from t-Bu, i-Pr, n-Bu, cyclohexyl, cyclopentyl, cyclohexylmethyl, cyclopentylmethyl, piperidinyl, and benzyl. 
     
     
         86 . (canceled) 
     
     
         87 . (canceled) 
     
     
         88 . A compound according to  claim 1  wherein the compound is selected from: 
       N-(benzo[d][1,3]dioxol-5-yl)-3-(1-tert-butyl-3-methyl-4-oxo-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-6-yl)azetidine-1-carboxamide; 
       3-(1-cyclohexyl-4-oxo-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-6-yl)-N-(4-(4-isopropylpiperazin-1-yl)phenyl)azetidine-1-carboxamide; 
       3-(1-cyclohexyl-4-oxo-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-6-yl)-N-(4-(4-methylpiperazin-1-yl)phenyl)azetidine-1-carboxamide; 
       3-(1-cyclohexyl-4-oxo-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-6-yl)-N-(3,4-dimethylphenyl)azetidine-1-carboxamide; 
       3-(1-cyclohexyl-4-oxo-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-6-yl)-N-(cyclohexylmethyl)azetidine-1-carboxamide; 
       3-(1-tert-butyl-3-methyl-4-oxo-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-6-yl)-N-phenylazetidine-1-carboxamide; 
       3-(1-cyclohexyl-4-oxo-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-6-yl)-N-(3-(dimethylamino)phenyl)azetidine-1-carboxamide; 
       N-(3-chlorophenyl)-3-(1-cyclohexyl-4-oxo-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-6-yl)azetidine-1-carboxamide; 
       3-(1-cyclohexyl-4-oxo-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-6-yl)-N-(4-(dimethylamino)phenyl)azetidine-1-carboxamide; 
       3-(1-cyclohexyl-4-oxo-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-6-yl)-N-(4-morpholinophenyl)azetidine-1-carboxamide; 
       3-(1-cyclohexyl-4-oxo-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-6-yl)-N-phenylazetidine-1-carboxamide; 
       3-(1-tert-butyl-3-methyl-4-oxo-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-6-yl)-N-(4-fluorophenyl)azetidine-1-carboxamide; 
       3-(1-cyclohexyl-4-oxo-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-6-yl)-N-(4-methoxyphenyl)azetidine-1-carboxamide; 
       3-(1-cyclohexyl-3-methyl-4-oxo-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-6-yl)-N-phenylazetidine-1-carboxamide; 
       3-(1-tert-butyl-3-methyl-4-oxo-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-6-yl)-N-cyclohexylazetidine-1-carboxamide; 
       3-(1-tert-butyl-4-oxo-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-6-yl)-N-(4-fluorophenyl)azetidine-1-carboxamide; 
       3-(1-tert-butyl-3-methyl-4-oxo-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-6-yl)-N-(4-fluorobenzyl)azetidine-1-carboxamide; 
       3-(1-cyclohexyl-4-oxo-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-6-yl)-N-(4-isopropylphenyl)azetidine-1-carboxamide; 
       3-(1-cyclohexyl-4-oxo-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-6-yl)-N-(4-fluorophenyl)azetidine-1-carboxamide; 
       3-(1-cyclohexyl-4-oxo-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-6-yl)-N-(3,4-difluorophenyl)azetidine-1-carboxamide; 
       3-(1-cyclohexyl-3-methyl-4-oxo-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-6-yl)-N-(4-fluorophenyl)azetidine-1-carboxamide; 
       N-benzyl-3-(1-tert-butyl-3-methyl-4-oxo-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-6-yl)azetidine-1-carboxamide; 
       N-cyclohexyl-3-(1-cyclohexyl-4-oxo-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-6-yl)azetidine-1-carboxamide; 
       N-benzyl-3-(1-cyclohexyl-3-methyl-4-oxo-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-6-yl)azetidine-1-carboxamide; 
       3-(1-cyclohexyl-4-oxo-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-6-yl)-N-(4-(trifluoromethoxy)phenyl)azetidine-1-carboxamide; 
       tert-butyl 3-(3-(1-cyclohexyl-4-oxo-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-6-yl)azetidine-1-carboxamido)piperidine-1-carboxylate; 
       3-(1-cyclohexyl-3-methyl-4-oxo-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-6-yl)-N-(4-fluorobenzyl)azetidine-1-carboxamide; 
       3-(1-cyclohexyl-3-methyl-4-oxo-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-6-yl)-N-(4-methoxybenzyl)azetidine-1-carboxamide; 
       N-(2-(difluoromethoxy)phenyl)-3-(1-(4-fluorophenyl)-3-methyl-4-oxo-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-6-yl)azetidine-1-carboxamide; 
       3-(1-cyclohexyl-4-oxo-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-6-yl)-N-(4-fluorobenzyl)azetidine-1-carboxamide; 
       N-benzyl-3-(1-cyclohexyl-4-oxo-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-6-yl)azetidine-1-carboxamide; 
       3-(1-cyclohexyl-4-oxo-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-6-yl)-N-cyclopentylazetidine-1-carboxamide; 
       N-(4-cyanophenyl)-3-(1-cyclohexyl-4-oxo-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-6-yl)azetidine-1-carboxamide; 
       N-butyl-3-(1-cyclohexyl-4-oxo-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-6-yl)azetidine-1-carboxamide; 
       3-(1-cyclohexyl-4-oxo-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-6-yl)-N-(4-(trifluoromethyl)phenyl)azetidine-1-carboxamide; 
       3-(1-cyclohexyl-4-oxo-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-6-yl)-N-(3,4-dichlorobenzyl)azetidine-1-carboxamide; 
       N-tert-butyl-3-(1-cyclohexyl-4-oxo-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-6-yl)azetidine-1-carboxamide; 
       3-(1-cyclohexyl-3-methyl-4-oxo-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-6-yl)-N-(3,4-dichlorobenzyl)azetidine-1-carboxamide; 
       3-(1-cyclohexyl-4-oxo-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-6-yl)-N-(1-(methylsulfonyl)piperidin-4-yl)azetidine-1-carboxamide; 
       tert-butyl 4-(3-(1-cyclohexyl-4-oxo-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-6-yl)azetidine-1-carboxamido)piperidine-1-carboxylate; 
       (S)-3-(1-cyclohexyl-3-methyl-4-oxo-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-6-yl)-N-(1-phenylethyl)azetidine-1-carboxamide; and 
       3-(1-cyclohexyl-4-oxo-4,5-dihydro-1H-pyrazolo[3,4-d]pyrimidin-6-yl)-N-(3,3,3-trifluoropropyl)azetidine-1-carboxamide;
 or a pharmaceutically acceptable salt thereof, and isotopic variants thereof, stereoisomers and tautomers thereof. 
 
     
     
         89 . (canceled) 
     
     
         90 . A pharmaceutical composition comprising a pharmaceutically acceptable carrier and a pharmaceutically effective amount of a compound according to  claim 1 . 
     
     
         91 . (canceled) 
     
     
         92 . (canceled) 
     
     
         93 . (canceled) 
     
     
         94 . (canceled) 
     
     
         95 . (canceled) 
     
     
         96 . (canceled) 
     
     
         97 . A method of treatment or prevention of diseases associated with bone and/or cartilage degradation, which comprises administering to a subject in need thereof, a therapeutically effective amount of a compound according to  claim 1 . 
     
     
         98 . A method of treatment or prevention of rheumatoid arthritis, which comprises administering to a subject in need thereof, a therapeutically effective amount of a compound according to  claim 1 . 
     
     
         99 . A method of treatment or prevention of osteoarthritis, which comprises administering to a subject in need thereof, a therapeutically effective amount of a compound according to  claim 1 .

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